146 research outputs found
Evidence for Quantum Interference in SAMs of Arylethynylene Thiolates in Tunneling Junctions with Eutectic Ga-In (EGaIn) Top-Contacts
This paper compares the current density (J) versus applied bias (V) of self-assembled monolayers (SAMs) of three different ethynylthiophenol-functionalized anthracene derivatives of approximately the same thickness with linear-conjugation (AC), cross-conjugation (AQ), and broken-conjugation (AH) using liquid eutectic Ga-In (EGaIn) supporting a native skin (~1 nm thick) of Ga2O3 as a nondamaging, conformal top-contact. This skin imparts non-Newtonian rheological properties that distinguish EGaIn from other top-contacts; however, it may also have limited the maximum values of J observed for AC. The measured values of J for AH and AQ are not significantly different (J ≈ 10-1 A/cm2 at V = 0.4 V). For AC, however, J is 1 (using log averages) or 2 (using Gaussian fits) orders of magnitude higher than for AH and AQ. These values are in good qualitative agreement with gDFTB calculations on single AC, AQ, and AH molecules chemisorbed between Au contacts that predict currents, I, that are 2 orders of magnitude higher for AC than for AH at 0 < |V| < 0.4 V. The calculations predict a higher value of I for AQ than for AH; however, the magnitude is highly dependent on the position of the Fermi energy, which cannot be calculated precisely. In this sense, the theoretical predictions and experimental conclusions agree that linearly conjugated AC is significantly more conductive than either cross-conjugated AQ or broken conjugate AH and that AQ and AH cannot necessarily be easily differentiated from each other. These observations are ascribed to quantum interference effects. The agreement between the theoretical predictions on single molecules and the measurements on SAMs suggest that molecule-molecule interactions do not play a significant role in the transport properties of AC, AQ, and AH.
Conductance statistics from a large array of sub-10 nm molecular junctions
Devices made of few molecules constitute the miniaturization limit that both
inorganic and organic-based electronics aspire to reach. However, integration
of millions of molecular junctions with less than 100 molecules each has been a
long technological challenge requiring well controlled nanometric electrodes.
Here we report molecular junctions fabricated on a large array of sub-10 nm
single crystal Au nanodots electrodes, a new approach that allows us to measure
the conductance of up to a million of junctions in a single conducting Atomic
Force Microscope (C-AFM) image. We observe two peaks of conductance for
alkylthiol molecules. Tunneling decay constant (beta) for alkanethiols, is in
the same range as previous studies. Energy position of molecular orbitals,
obtained by transient voltage spectroscopy, varies from peak to peak, in
correlation with conductance values.Comment: ACS Nano (in press
Climate Change Alters Seedling Emergence and Establishment in an Old-Field Ecosystem
Background: Ecological succession drives large-scale changes in ecosystem composition over time, but the mechanisms whereby climatic change might alter succession remain unresolved. Here, we asked if the effects of atmospheric and climatic change would alter tree seedling emergence and establishment in an old-field ecosystem, recognizing that small shifts in rates of seedling emergence and establishment of different species may have long-term repercussions on the transition of fields to forests in the future. Methodology/Principal Findings: We introduced seeds from three early successional tree species into constructed old-field plant communities that had been subjected for 4 years to altered temperature, precipitation, and atmospheric CO 2 regimes in an experimental facility. Our experiment revealed that different combinations of atmospheric CO2 concentration, air temperature, and soil moisture altered seedling emergence and establishment. Treatments directly and indirectly affected soil moisture, which was the best predictor of seedling establishment, though treatment effects differed among species. Conclusions: The observed impacts, coupled with variations in the timing of seed arrival, are demonstrated as predictors o
Temperature and force dependence of nanoscale electron transport via the Cu protein Azurin
The mechanisms of solid-state electron transport (ETp) via a monolayer of
immobilized Azurin (Az) was examined by conducting probe atomic force
microscopy (CP-AFM), both as function of temperature (248 - 373K) and of
applied tip force (6-12 nN). By varying both temperature and force in CP-AFM,
we find that the ETp mechanism can alter with a change in the force applied via
the tip to the proteins. As the applied force increases, ETp via Az changes
from temperature-independent to thermally activated at high temperatures. This
is in contrast to the Cu-depleted form of Az (apo-Az), where increasing the
applied force causes only small quantitative effects, that fit with a decrease
in electrode spacing. At low force ETp via holo-Az is temperature-independent
and thermally activated via apo-Az. This observation agrees with
macroscopic-scale measurements, thus confirming that the difference in ETp
dependence on temperature between holo- and apo-Az is an inherent one that may
reflect a difference in rigidity between the two forms. An important
implication of these results, which depend on CP-AFM measurements over a
significant temperature range, is that for ETp measurements on floppy systems,
such as proteins, the stress applied to the sample should be kept constant or,
at least controlled during measurement.Comment: 24 pages, 6 figures, plus Supporting Information with 4 pages and 2
figure
High on-off conductance switching ratio in optically-driven self-assembled conjugated molecular systems
A new azobenzene-thiophene molecular switch is designed, synthesized and used
to form self-assembled monolayers (SAM) on gold. An "on/off" conductance ratio
up to 7x1E3 (with an average value of 1.5x1E3) is reported. The "on"
conductance state is clearly identified to the cis isomer of the azobenzene
moiety. The high "on/off" ratio is explained in terms of photo-induced,
configuration-related, changes in the electrode-molecule interface energetics
(changes in the energy position of the molecular orbitals with respect to the
Fermi energy of electrodes) in addition to changes in the tunnel barrier length
(length of the molecules). First principles DFT calculations demonstrate a
better delocalization of the frontier orbitals, as well as a stronger
electronic coupling between the azobenzene moiety and the electrode for the cis
configuration over the trans one. Measured photoionization cross-sections for
the molecules in the SAM are close to the known values for azobenzene
derivatives in solution.Comment: 1 file with main text, figure and suppementary informatio
Characterizing the Metal–SAM Interface in Tunneling Junctions
his paper investigates the influence of the interface between a gold or silver metal electrode and an n-alkyl SAM (supported on that electrode) on the rate of charge transport across junctions with structure Met(Au or Ag)TS/A(CH2)nH//Ga2O3/EGaIn by comparing measurements of current density, J(V), for Met/AR = Au/thiolate (Au/SR), Ag/thiolate (Ag/SR), Ag/carboxylate (Ag/O2CR), and Au/acetylene (Au/C≡CR), where R is an n-alkyl group. Values of J0 and β (from the Simmons equation) were indistinguishable for these four interfaces. Since the anchoring groups, A, have large differences in their physical and electronic properties, the observation that they are indistinguishable in their influence on the injection current, J0 (V = 0.5) indicates that these four Met/A interfaces do not contribute to the shape of the tunneling barrier in a way that influences J(V).Chemistry and Chemical Biolog
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